Vat dyestuffs of the anthraquinone series



Patented Feb. 14, 1939 PATENT OFFICE VAT DYESTUFFS OF THE ANTHRAQUINONESERIES Erich Berthold and Joachim Mueller, Ludwigshafen-on-the-Rln'ne,Germany, assignors to General Aniline Works, Inc., New York, N. Y., acorporation of Delaware No Drawing. Application March 9, 1937, SerialNo. 129,818. In Germany February 1, 1934 5 Claims.

The present invention relates to vat dyestufis of the anthraquinoneseries. The application is a continuation-impart of our copendingapplication Ser. No. 3,190 filed January 23, 1935.

We have found that valuable vat dyestufis of the anthraquinone seriesare obtained by preparing aminoanthraquinoneoxazoles having the generalformula /O\ Y o R NH-CO-R1 in which R stands for the radical of ananthraquinone and R1 for a vattable radical, and which may containfurther amino or acylamino groups in at least one of the anthraquinoneradicals.

A great variety of methods may be employed for the preparation of thedyestuffs according to this invention. Thus, for example, l-amino-4-anthraquinone (0') ylamino 2 anthraquinonyl- 2.3-anthraquinoneoxazolehaving the formula Co a? i Y O o H may be prepared as follows:

l-amino-l-halogenor 1-amino-4-nitroanthraquinone 2 carbonylamino2.3-hydroxyanthraquinone (obtainable by the condensation ofl-aminol-halogenor l-amino-l-nitroanthraquinone-Z-carboxylic acidchloride with 2- amino3-hydroxyanthraquinone) is converted by heatingwith ammonia or by reaction with paratoluene sulphamide and subsequentsaponification or by reduction intolA-diaminoanthraquinone-Z-carbonylamino- 2'.3 hydroxyanthraquinone. Byring closure by means of acid condensing agents, such as sulfuric acidor para-toluene sulfonic acid, there is obtained therefrom 1.4-diamino2anthraquinonyl-2'.3- anthraquinoneoxazole. The 1-amino-4-halogenor1-amino-4-nitroanthraquinone 2 carbonylamino-2C3-hydroxyanthraquinonemay also be first converted into the corresponding oxazole derivative,the halogen or nitro groups then being replaced by amino groups. Bycondensing l-amino-4-nitroanthraquinone-2-aldehyde 'with2-amino-3-hydroxyanthraquinone, for example in nitrobenzene in thepresent of potassium acetate, 1-amino-4-nitro-2-anthraquinonyl-2'.3-anthraquinoneoxazole is obtained which can be converted into thecorresponding diaminooxazole in the manner already described.Corresponding products 'may also be obtained by nitration oi 1-amino-2-anthraquinonyl-2,3-anthraquinoneoxazole and subsequent reductionof the resulting nitro compounds. ThelA-diamino-Z-anthraquinonyl-2.3-anthraquinoneoxazole is then convertedinto the dyestufi having the formula above mentioned by acting thereonwith the chloride of anthraquinone-2-carboxylic acid.

Other vat dyestuffs of the said kind may be prepared in an analogousmanner.

Thus, for example, the halids of other carboxylic acids of vattablecompounds may be employed instead of the chloride of anthraquinone-Z-carboxylic acid, for example the chlorides or bromides of carboxylicacids of other anthraquinonic bodies such as anthraquinoneacridones,pyridonoanthraquinones or anthraquinonethioxanthones, furthermore ofpyrazolanthrones, thiazoleanthrones, pyridanthrones, anthrapyridines oranthrapyrimidones.

The vat dyestuffsthus obtainable have good properties as regardsfastness, dye vegetable fibres usually in red to green shades dependingon the number of the amino and/or acylamino groups and their position inthe molecule. The dyestuffs according to this invention may also beprepared by causing initial materials of the said kind containinghalogen to react with acid amides, as for example benzamide or toluenesulfamide.

The following examples will further illustrate how the said inventionmay be carried out in practice but the invention is not restricted tothese examples. The parts are by weight.

Example 1 40 parts of 1-amino-4-nitro-2-anthraquinonyl-2.3-anthraquinoneoxazole (prepared for example by condensation of1-amino-4-nitroanthraquinone 2 carboxylic acid chloride with 2amino-3-hydroxyanthraquinone and conversion of the resulting1-amino-4-nitroanthraquinone- 2 carbonylamino 2'3 hydroxyanthraquinoneinto the corresponding oxazole derivatives by treating with para-toluenesulfonic acid) are heated in the form of a paste with 2000 parts ofwater and 8 parts of sodium sulfide while stirring at 90 C. untilinitial material can no longer be detected. The whole is filtered off bysuction and freed from sodium sulfide by washing with water. The1.4-diamino-2-anthraquinonyl-2'.3- anthraquinoneoxazole obtained is aviolet-blue powder which dissolves in concentrated sulfuric acid givingan olive-green coloration and dyes cotton greenish blue shades from abrown-violet vat.

The reduction may also be efi'ected for example with hydrazine hydratein nitrobenzene. The diamino derivative is then obtained in the form ofblue-violet leaflets. If dimethylaniline or another amine of highboiling point such as aniline, toluidine or beta-naphthylamine, beemployed instead of hydrazine hydrate, the diamino derivative is alsoobtained in a pure form. The same compound is also obtained for exampleby reducing 1 amino-4-nitroanthraquinone-2 -carbonylamino-2'3hydroxyanthraquinone with hydrazine hydrate and converting the resulting1.4-diaminoanthraquinone-2-carbonylamino -2' .3-hydroxyanthraquinoneinto the corresponding oxazole derivative.

A mixture of 24 parts of the 1.4-diamino-2-anthraquinonyl 2.3'anthraquinoneoxazole prepared according to the first paragraph, 25 partsof anthraquinone-2-carboxylic acid chloride, 500 parts of nitrobenzeneand 3 parts of anhydrous pyridine is slowly heated at 150 C. Heating iscontinued until initial material is no longer detectable. After workingup, blue-violet needles are obtained which dissolve in concentratedsulfuric acid giving a brown-yellow coloration dyeing vegetable fibresgrey-blue shades of excellent iastness to light from a violet vat.

By employing 1chloranthraquinone-2-carboxylic acid chloride or1.4-dichloranthraquinone-2- carboxylic acid chloride or 1.4dichloranthraquinone-G-carboxylic acid chloride instead ofanthraquinone-2-carboxylic acid chloride similar dyestuffs are obtainedwhich dye vegetable fibres likewise grey-blue shades of excellentfastness properties.

By employing l-aminoanthraquinone 2 carboxylic acid chloride a dyestuffis obtained which dyes vegetable fibres violet shades.

By the reduction of l-amino 4 nitro 2 anthraquinonyl-6-chlor- 2..3'anthraquinoneoxazole of the formula by means of sodium sulfide or thelike 1.4 di amino-2-anthraquinonyl-6'-chlor- 2.3'- anthraquinoneoxazoleis obtained the acylation prodnets with halides of anthraquinonecarboxylic acids of which prepared in a manner corresponding to thatdescribed in the preceding paragraph have similar properties.

Example 2 10 parts of l-amino-4-nitro-2-anthraquinonyl- 1(N)-2(O)anthraquinoneoxazole (obtainable for example by the condensation ofl-aminolnitroanthraquinone 2 --carboxylic acid chloride with1-amino-2-hydroxyanthraquinone and ring closure to form the oxazole in amanner analogous to that described in Example 1) are reduced in 500parts of water with 20 parts of sodium sulfide in the manner describedin Example 1. The 1.4-diamino-2-anthraquinonyl- 1 (N) -2' (0)-anthraquinoneoxazole thus obtained is a red-blue powder which dissolvesin concentrated sulfuric acid giving an orange coloration and dyescotton greenish blue shades from a red-violet vat.

Starting from 1-amino-4-nitro-2-anthraquinopyl-3-ch1or 1 (N) -2 (O)-anthraquinoneoxazole (obtainable for example by the condensation of1-amino-4-nitroanthraquinone-2-carboxylic acid chloride with1-amino-2-hydroxy-3-chloroanthraquinone and ring closure to form theoxazole according to Example 1) there is obtained by reduction, as forexample with alkaline hydrosulfite, the corresponding 1.4diamino-Z-anthraquinonyl-3-chlor- 1'(N) -2(O) anthraquinoneoxazole whichdyes cotton powerful greenish blue shades from a red-violet vat.

The products obtainable according to the pre ceding paragraphs are thenacylated in a manner corresponding to that described in Example 1 bymeans of anthraquinone-1(N)-2-1'.2'(N) benzacridone-5- or 3-carboxylicacid chloride. The dyestufis thus formed are crystalline powders whichdye vegetable fibres reddish grey shades from violet vats of excellentfastness properties especially against chlorine.

Example 3 NQ O NHz O is filtered off by suction, washed with benzene andmethanol and dried. It dissolves in concentrated sulfuric acid giving abrown-yellow coloration and dyes vegetable fibres reddish violet shadesof very good fastness from a blue-red vat.

Example 4 A mixture of 12 parts of the oxazole obtainable according tothe first paragraph of Example 1, 10 parts of anthraq'uinone-MN).2-1'.2(N) -benzacridone-5' -carboxy1ic acid chloride, 250 parts ofnitrobenzene and 1 part of pyridine is heated at from 180 to 200 C.until initial material is no longer detectable. After Working up, adyestufi is obtained in the form of blue crystals which dyes vegetablefibres reddish grey shades from a violet vat.

By employing anthraquinone-I (N) .2-1'.2 (N) benzacridone-3-carboxylicacid chloride a dyestulf having similar properties is obtained.

Similar dyestuffs are obtained by employing1.Q-pyrazoleanthrone-Z-carboxylic acid chloride.

Example 5 Example 6 A mixture of 10 parts of1.4-diamino-2-anthraquinonyl-1(O) .2 (N) -anthraquinoneoxazole(obtainable by condensing 1-amino-4-nitroanthraquinone-Z-carboxylic acidchloride with 1-hydroxy-Z-aminoanthraquinone, ring closure withpara-toluene-sulphonic acid in the presence of nitrobenzene andreduction by means of sodium sulphide), 10 parts of1.4-dichloranthraquinone- Z-carboxylic acid chloride and 300 parts ofnitrobenzene is heated at from to 200 C., until initial material is nolonger detectable. After working up the dyestuff formed is isolated inthe usual manner. It dyes vegetable fibres fast bluegrey shades from aviolet vat.

What we claim is:

1. Vat dyestuffs of the general formula wherein R1 stands for a nuclearradical having an anthraquinone nucleus, a ring of the said nuclearradical being directly combined with the CO- group.

2. Vat dyestuifs of the general formula W NH.CO.R1

wherein R1 stands for the radical of an anthraquinoneacridone and Rstands for an anthraquinone radical, a ring of the saidanthraquinoneacridone radical marked R1 being directly combined with theCO-group.

3. The vat dyestuff of the formula NH-CO- n I O I Y c O NH2 4. The vatdyestufi of the formula 5. The vat dyestuff of the formula o I \N ERICHBERTHOLD. JOACHIM MUELLER.

